EP3294692A1 - Procédé d'oligomérisation d'oléfines par polymérisation par transfert de chaîne et coordination - Google Patents

Procédé d'oligomérisation d'oléfines par polymérisation par transfert de chaîne et coordination

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Publication number
EP3294692A1
EP3294692A1 EP16732224.7A EP16732224A EP3294692A1 EP 3294692 A1 EP3294692 A1 EP 3294692A1 EP 16732224 A EP16732224 A EP 16732224A EP 3294692 A1 EP3294692 A1 EP 3294692A1
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EP
European Patent Office
Prior art keywords
catalyst
csa
process according
cctp
chain
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP16732224.7A
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German (de)
English (en)
Inventor
Albert BODDIEN
Rhett Kempe
Winfried Kretschmer
Andreas Gollwitzer
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Sasol Performance Chemicals GmbH
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Sasol Performance Chemicals GmbH
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Priority claimed from EP15167707.7A external-priority patent/EP3093280A1/fr
Priority claimed from GBGB1512872.1A external-priority patent/GB201512872D0/en
Application filed by Sasol Performance Chemicals GmbH filed Critical Sasol Performance Chemicals GmbH
Publication of EP3294692A1 publication Critical patent/EP3294692A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/122—Metal aryl or alkyl compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
    • C07C2/88—Growth and elimination reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
    • B01J2231/12—Olefin polymerisation or copolymerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/48—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/49—Hafnium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

Definitions

  • the oligomerisation of olefins can yield product distributions with regard to chain lengths which are either Gauss or Poisson distributions or Schulz-Flory distributions.
  • a Gauss or Poisson distribution is a normal distribution curve approximately centred at the average degree of oligomerisation.
  • a Schulz-Flory distribution describes a product distribution having a greater molar amount of the small oligomers with a broader range of chain lengths.
  • For short chain oligomers C ⁇ 12 mainly Schulz-Flory distributions are desired, however, if chain length above C12 are requested Poisson distributed products are often desired.
  • a Gaussian distribution is characterized by the following formula:
  • the middle olefin fractions such as 1-decene, 1-do- decene and -tetradecene are used as raw materials for the production of synthetic oils, detergents and shampoos.
  • the heavy olefin fractions can be used as additives for lubricating oils, surfactants, oil field chemicals, waxes and as polymer compati- bilisers.
  • coal reacts at very high temperatures (above 1000°C) with water vapour and oxygen to form synthesis gas which, after separation of nitrogen oxides and sulphur dioxide, is reacted via heterogeneous catalysis to form hydrocarbons including alpha-olefins and water.
  • synthesis gas which, after separation of nitrogen oxides and sulphur dioxide, is reacted via heterogeneous catalysis to form hydrocarbons including alpha-olefins and water.
  • natural gas is reacted via addition of oxygen and water vapour to form synthesis gas, and the latter is transformed into hydrocarbons in a Fischer- Tropsch-Synthesis.
  • Both processes have the disadvantage that a broad variety of byproducts, such as paraffins and alcohols, are produced. This means that more pure alpha-olefins become accessible only after purification processes (e.g. DE 10022466 A1).
  • alpha-olefins Other industrial-scale procedures for the preparation of alpha-olefins are the cracking of paraffins, the dehydrogenation of paraffins and the dehydration of alcohols, decarboxylation of lactones and fatty acids, or chain growth reactions including the oligomerisation of ethylene (e.g. US 20140155666A1). Since ethylene represents an easily available raw material, the first mentioned methods of production play a minor role. The vast majority of alpha-olefins are produced via oligomerisation of ethylene providing exclusively olefins with an even number of C-atoms which have the highest value for commercial applications (e.g. G. J. P. Britovsek et al., Angew. Chem. Int. Ed.
  • LAO's which are based on the oligomerisation of ethylene are the following: - the oligomerisation reaction in the Shell Higher-Olefin-Process (SHOP;) using a nickel complex, providing exclusively a Schulz-Flory distribution from the oligomerisation reaction;
  • SHOP Shell Higher-Olefin-Process
  • CCTP coordinative chain transfer polymerisation
  • transition metal based CCTP catalysts are typically used together with co-catalysts which usually act as chain shuttling agent (CSA).
  • CSA chain shuttling agent
  • Suitable co-catalysts include alkylzinc, alkylaluminium, alkylaluminium halides and alkyl alumoxanes, commonly used in combination with inert, non-coordinating ion forming compounds (activators), Lewis and Bronstedt acids and mixtures thereof.
  • CCTP One characteristics of CCTP is that the resulting polymer chains are end-capped with the respective main group metal of the co-catalyst and can be further function- alised (M. Bialek, J. Polym. Sci.: Part A: Polym. Chem. 2010, 48, 3209-3214 and W. P. Kretschmer et al., Dalton Trans. 2010, 39, 6847-6852).
  • Nearly all previously reported catalytic systems suffer from ligand transfer from the CCTP catalyst complex onto the CSA and are therefore not stable at high CSA concentrations.
  • CCTP typically requires the use of a metal complex as catalyst, a co-catalyst and optionally an activator.
  • the co-catalyst is a chain shuttling agent (CSA) and may optionally, but not necessarily, be an acti- vator at the same time.
  • the activator can be for example a compound different from the chain transfer agent that is not functioning as a chain shuttling agent. Such activator is herein solely named “activator” and is not called a "co-catalyst".
  • the invention makes use of a CCTP catalyst system operating preferably at temperatures between 20-200 °C which comprises a metal organic complex capable of oligomerising or co-oligomerising alpha-olefins as gases or liquids, an activator, at least one chain shuttling agent (CSA), which is capable of transferring the alkyl chain at the catalyst onto the chain shuttling agent, and a chain-displacement-catalyst (CDC) capable of catalysing the beta-H-elimination and if necessary isomerisation to finally obtain olefins (alpha and/or internal olefins) with a controlled chain length distribution.
  • CSA chain shuttling agent
  • CDC chain-displacement-catalyst
  • CCTP in situ use of the two catalysts
  • CDC CSA
  • the obtained olefins can vary in chain length and distribution, which depends on CCTP, CSA(1 ), CSA(2), CDC, ratios and the process conditions applied.
  • the oligomerised olefins obtained are C4 to C80 olefins, most preferably C16 to C30 olefins.
  • the further embodiment of the present invention following a dual chain shuttling mechanism uses a mixture of a zinc hydrocarbyl compound with a metal alkyl from the groups XII and XIII, preferably trialkylaluminium as chain transfer agents.
  • the zinc hydrocarbyl compound enhances the chain transfer rate, which results in an increase of the chain transfer (Kt) to chain growing (K P ) ratio to better tune the chain lengths of the produced alpha-olefins.
  • Increasing amounts of zinc hydrocarbyl compounds give shorter chain length and vice versa.
  • CCTP catalysts The stability, selectivity, and the activity of a variety of activated CCTP catalysts are enhanced.
  • the proposed mechanism for the first embodiment is displayed in Fig 1 and for dual chain shuttling in Fig 1a, wherein M stands for the CCTP catalyst; CSA(1) and CSA(2) for the chain shuttling agents; diethylzinc as CSA (1) and triethylaluminium as CSA (2) are shown as examples; as CDC (chain displacement catalyst) in Fig. 1a Ni(cyclooctadiene)2 is shown as example.
  • the mechanism displayed in Fig.1a. differs from the mechanism displayed in Fig. 1 , in that the oligomeric chain is no longer liberated from the CSA by the CDC but an intermediate CSA(2) cycle is used so that the CSA(1 ) transfers the oligomeric chain first to the CSA(2) whereupon the CDC liberates the olefin generated from the CSA(2).
  • a fast alkyl exchange with the CSA(2) e.g. triethyl aluminum
  • transports the oligomeric chain to the CDC e.g. bis(1 ,5-cyclooctadiene)nickel(0), which replaces the oligomer by an ethyl group.
  • Item 7 The process according to any one of the preceding items wherein the chain shuttling agent (CSA) is a C1 to C30 hydrocarbyl metal compound, methylalumox- ane or both, the metal being aluminium, zinc, magnesium, indium or gallium, pref- erably tri hydrocarbyl aluminium, dihydrocarbyl magnesium or dihydrocarbyl zinc.
  • CSA chain shuttling agent
  • Item 11 The process according to any one of the preceding items wherein the molar ratio of the coordinative chain transfer polymerisation catalyst (CCTP catalyst) to the chain displacement catalyst (CDC)
  • Item 16 The process according to one or more of the preceding items, wherein the coordinative chain transfer polymerisation catalyst comprises as transition metal Ti, Zr or Hf and one ligand per metal of the following formula
  • Z1 , Z2 and Z3 independently from each other are optionally linked with one or more of each other, and
  • CCTP catalyst coordinative chain transfer polymerisation catalyst
  • Item 20 A process for the manufacture of a di- -halogen-bridged bis guanidinato tetrahalogen di zirconium compound comprising the following steps:
  • R 3 ,R 4 independent from each x, y is hydrocarbyl, in particular alkyl, or halogen, wherein R is preferably substituted at the 2 or 6 position of the aryl, and further wherein R is branched at the 2-position
  • Ar is aryl, optionally substituted, in particular benzene.
  • R 1 ,R 2 being C1 to C40 hydrocarbyl-, optionally comprising one or more het- eroatoms, wherein the heteroatom is not adjacent to the N-Atom;
  • R 3 ,R 4 independent from each x, y is hydrocarbyl, in particular alkyl, or halogen, wherein R is preferably substituted at the 2 or 6 position of the aryl, and further wherein R is branched at the 2-position;
  • Item 22 The process according to item 20 or 21 wherein the reaction is carried out in a hydrocarbon solvent in particular an aromatic solvent, preferably at temperatures of 30 to 100°C, in particular 40 to 90°C.
  • Item 23 The process according to one of items 20 to 22 wherein the di-p-halogen- bridged bis guanidinato tetrahalogen di zirconium compound, preferably as further defined under item 21 , is obtained by precipitation, preferably by crystallisation.
  • the di-p-halogen-bridged bis guanidinato tetrahalogen di zirconium compound preferably as further defined under item 21 , is obtainable by the process of any of items 20 to 23
  • the Grignard-reagent is alkyl Mg Hal, wherein
  • Alkyl is C1 to C20 alkyl, in particular methyl or ethyl.
  • Item 26 The process of item 24 or 25 wherein the zirconium guanidinato alkyl compound is
  • Item 27 The process according to any one of items 24 to 26
  • zirconium guanidinato alkyl compound is obtained by precipitation, preferably by crystallisation.
  • R3 i is independently from each other zero to three hydrocarbyl, in particular alkyl moieties
  • Useful ligands, one or two per transition metal are selected from cyclopentadienyl, indenyl, fluorine, diamide ligands, phenoxy-imine-ligand, in- dolide-imine-ligands, amidinate, guanidinate, amidopyridine, pyridinimine and alco- holate each optionally substituted.
  • preferred metals are Ti, Zr or Hf in the +2, +3 or +4 formal oxidation state, preferably in the +4 formal oxidation state.
  • a particularly preferred ligand is a guanidine-based metal-complex comprising one of the following ligands:
  • the metal complex has the following structure:
  • the metal complexes preferably have the following structure
  • M Ti, Zr or Hf, preferably Ti or Zr, more preferably Zr,
  • X halogene, preferably CI, more preferably hydrocarbyl, in particular methyl, R1 , R2 as defined above.
  • R3 is a hydrocarbon moiety, in particular C1 to C40, preferably C1 to C 8, optionally substituted hydrocarbon moiety additionally comprising one or more nitrogen, oxygen, and/or silicon atom(s).
  • the above mentioned complexes may also exist as anionic species with an additional cation Q + which for example is selected from the group of R N + , R3 H + , R2NH2 + , RNH3 + , NhV, R4P + in which R is an alkyl, aryl, phenyl, hydrogen or halogen.
  • the transition metal precursor may be any Ti, Zr or Hf c3 ⁇ 4nplex capable of reacting with a Iigand precursor to form a guanidinate complex or hydrocarbyl-2- pyridyl amine complex as described above in situ.
  • each X may independently halogen ⁇ F, CI, Br, I ⁇ , hydride ⁇ H ⁇ , hydrocarbyl ⁇ R, e.g. benzyl ⁇ , alkoxide ⁇ OR ⁇ or amide ⁇ NR1 R2 ⁇ );
  • each X may independently halogen ⁇ F, CI, Br, I ⁇ , hydride ⁇ H ⁇ , hydrocarbyl ⁇ R, e.g. benzyl ⁇ , alkoxide ⁇ OR ⁇ or amide ⁇ NR R2 ⁇ with L equals any two electron donor Iigand, e.g. ethers such as tetrahydrofuran,or diethy- letherf, acetonitrile, or trihydrocarbylphosphine;
  • acac 2,4-pentanedionato, 1 ,1 , 1 ,5,5, 5-hexafluoro-2,4-pen- tanedionato or 2,2,6,6-tetramethyl-3,5-heptanedionato;
  • O2CR is any carboxylic acid anion, e.g. 2-ethylhexanoate.
  • the Iigand precursor may be any compound capable of reacting with a transition metal precursor to form an amidine or guanidine complex or the cyclopentadienyl and the hydrocarbyl-2-pyridyl amine Iigand in situ.
  • Examples of such Iigand precursor include:
  • dihydrocarbylcarbodiimides such as bis(2,6-diisopropylphenyl)carbodiimide or dicyclohexylcarbodiimide, diheterohydrocarbylcarbodiimides, such as bis(2-methoxyphenyl)car- bodiimide;
  • amidate or guanidate salts e.g. lithium 1 ,3-dihydrocarbylamidate or lithium 1 ,3-dihydrocarbylguanidate;
  • guanidines such as 2,3-bis(2,6-diisopropylphenyl)-1 ,1-dihydrocarbylguani- dine; or
  • 2-pyridine amines or 6-pyridine amines such as
  • the co-catalyst acts as a chain shuttling agent and may optionally act in addition as an activator for the complex in order that the complex becomes the (active) catalyst.
  • di-substituted oxonium salts such as: diphenyloxonium tetrakis(pentafluorophenyl) borate, di(o T tolyl)oxonium tetrakis(pentafluorophenyl) borate, and di(2,6-dimethyl- phenyl)oxonium tetrakis(pentafluorophenyl) borate;
  • di-substituted sulfonium salts such as: diphenylsulfonium tetrakis(pentafluoro- phenyl) borate, di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, and bis(2,6- dimethylphenyl)sulfonium tetrakis(pentafluorophenyl) borate.
  • the activator may alternatively comprise an aluminium containing compound such as an aluminate. More preferably the activator comprises an tetrakisalkyloxy-alumi- nate or tetrakisaryloxy-aluminate, in particular tetrakis-C1 to C6-alkyloxy-aluminate or tetrakisaryloxy-aluminate, the alky or aryl being -CF3 substituted, such as [AI(OC(Ph)(CF 3 )2)4]- or [AI(OC(CF 3 ) 3 )4]-.
  • an aluminium containing compound such as an aluminate. More preferably the activator comprises an tetrakisalkyloxy-alumi- nate or tetrakisaryloxy-aluminate, in particular tetrakis-C1 to C6-alkyloxy-aluminate or tetrakisaryloxy-aluminate,
  • the CSA a chain shuttling agent (CSA) being one or more metal alkyls selected from the group II, XII and XIII from the periodic table.
  • the CSA preferably is a C1 to C30 hydrocarbyl metal compound, methylaluminoxane or both, the metal being aluminium, zinc, magnesium, indium or gallium, preferably trihydrocarbyl aluminium, dihydrocarbyl magnesium or dihydrocarbyl zinc, preferrably zink dialkyl.
  • the CSAs are preferably Zn alkyl compounds (CSA(1)) and the other being one or more XIII metal alkyl (CSA(2)) preferably aluminium alkyls, most preferably triethylaluminium, Most preferably the CSA or CSAs (CSA (1), CSA (2)) (co-catalysts) are selected from:
  • hydrocarbyl aluminium is for example methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl or isopentyl or a mixtures thereof, preferably tri(methyl and/or ethyl) aluminium,
  • di-hydrocarbyl zinc wherein the hydrocarbyl is for example methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl or isopentyl or a mixtures thereof, preferably di(methyl and/or ethyl) zinc, or any other zinc compund that forms under reaction conditions zinc dihydrocarbyl compounds, a mixture of tri hydrocarbyl aluminium and di-hydrocarbyl zinc reagents as described above,
  • oligomeric or polymeric hydrocarbyl alumoxanes preferably oligomeric or polymeric methyl alumoxanes (including modified methylalumoxane, modified by reaction of methylalumoxane with triisobutyl aluminium or isobutyl- alumoxane), and for single CSA activation, not dual CSA:
  • hydrocarbyl aluminium halogenides such as dialkyl aluminium halogenides, alkyl aluminium dihalogenides, with alkyl preferably being C1 to C3-alkly, hydrocarbyl aluminium sesqui halogenides, preferably, methyl aluminium sesqui halogenides, di-hydrocarbyl magnesium, wherein the hydrocarbyl is for example methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl or isopentyl or a mixtures thereof, preferably di(methyl and/or ethyl and/or butyl) magnesium; tri-hydrocarbyl indium, wherein the hydrocarbyl is for example methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl or isopentyl or a mixtures thereof, preferably tri
  • tri-hydrocarbyl gallium wherein the hydrocarbyl is for example methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl or isopentyl or a mixtures thereof, preferably tri(methyl and/or ethyl and/or butyl) gallium or mixture thereof.
  • the most preferred CSA (acting also as co-catalyst) for use in forming the (active) catalysts is triethylaluminium or a mixture of triethylaluminium comprising minor portions of diethylaluminiumhydrid (such as below 10 wt.%).
  • the inventors assume without limiting the invention thereto that the zinc hydrocarbyl compound (CSA(1)) transfers the chains from and to the CCTP catalyst and that zinc hydrocarbyl compounds increase the chain transfer rate. This results in an increase of the chain transfer (Kt) to chain growing (K P ) ratio.
  • the aluminum hydrocarbyl CSA(2) is be- lieved to shuttle the chains from CSA(1 ) to the chain displacement catalyst.
  • the active CCTP catalysts are rendered catalytically active by combination of a CCTP catalyst (see 1.0 CCTP catalyst and ligands) with a) an activating co-catalyst (CSA) (on its own) or b) by a combination of a co-catalyst (CSA) with an activator as listed under 2.0 activator.
  • a CCTP catalyst see 1.0 CCTP catalyst and ligands
  • CSA activating co-catalyst
  • CSA co-catalyst
  • CSA co-catalyst
  • an activator can be used or is preferably to be used when the co-catalyst on its own is not activating. If the respective co- catalyst is selected from the trialkyl aluminium compounds use of activator is preferable. Suitable activators are referenced above.
  • the molar ratio of catalyst (CCTP catalyst) to co-catalyst (CSA) with reference to the [metal catalyst] to [CSA] atomic ratio preferably is from 1 : 1 to 1 : 10000000, more preferably 1 : 00 to 1 :100000 and most preferably 1 :1000 to 1 :40000.
  • CCTP catalyst co-catalyst
  • CSA co-catalyst
  • CDC Chain displacement Catalyst
  • the chain displacement catalyst is a nickel or cobalt compound.
  • Typical compounds are nickel and cobalt compounds with one or more of the following substituent: hal- ides, carbonyls, acetylacetonato, cyclooocta-1 ,5-diene, cyclopentadienyl, C1- to C12- octanoates, tri(C1- to C12- hydrocarbyQ-phosphines.
  • a support especially silica, alumina, magnesium chloride, or a polymer (especially poly(tetrafluoroethylene or a polyolefin) may also be applied.
  • the support is preferably used in an amount to provide a weight ratio of catalyst (based on metal): sup- port from 1 : 100000 to 1 : 10, more preferably from 1 :50000 to 1 :20, and most preferably from 1 :10000 to 1 :30.
  • Suitable solvents for oligomerisation are preferably inert liquids.
  • Suitable solvents include aliphatic and aromatic hydrocarbons, particularly C4 to C20 hydrocarbons or olefins, linear and/or branched, and mixtures thereof (including monomers subject to oligomerisation, especially the previously mentioned addition polymerisable monomers and produced oligomerised olefins); cyclic and alcyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; isooctanes, aromatic and hydrocarbyl-substituted aromatic compounds such as benzene, toluene, and xylene. Mixtures of the foregoing are also suitable. Most preferred is toluene. 9.0 Olefins
  • C1- to C8-olefins particularly alpha olefins, especially ethylene or ethylene and propylene or propylene are converted to oligomeric mono-unsaturated hydrocarbons, in short herein called oligomerised olefins.
  • oligomerised olefins oligomeric mono-unsaturated hydrocarbons
  • CSAs if dual chain shuttling is applied at least two CSAs one being one or more Zn hydrocarbyl compounds (CSA(1)), preferably dihydrocarbyl zinc, the other being one or more XIII metal hydrocarbyls (CSA(2)) preferably aluminium alkyls, most preferably triethylaluminium,
  • the growth composition contains further before or during the oligomerisation the chain displacement catalyst (CDC) according to one embodiment (simultaneous process )
  • the products obtained are the oligomerised olefins described herein below.
  • Nev- ertheless typically a solvent is provided first and the solvent is saturated with the olefin.
  • Suspension, solution, slurry, gas phase, solid state powder oligomerisation or other process condition may be applied as desired.
  • the oligomerisation may be accomplished at temperatures from 20 to 200 °C, preferably 50 to 100 °C, most preferably 60-90 °C, and pressures from 1 to 100 bar, preferably 1 to 30 bar.
  • pressures from 1 to 100 bar, preferably 1 to 30 bar.
  • shorter olefins can be produced if the reaction temperature is increased and pressure is decreased.
  • the distribution can be shifted from Schulz-Flory to Poisson or Gaussian via the applied CCTP catalyst system, the CSA, the activator and displacement catalyst.
  • the distribution can additionally be tuned by the catalyst:CSA:CDC ratio, and furthermore for the dual chain shuttling reaction mode by the CSA(1):CSA(2) ratio.
  • the distribution can also be altered via temperature and applied pressure.
  • the produced olefins can be purified via mechanical or thermal purification processes. In general filtration and distillation can be applied for purification purposes.
  • the olefin is obtained in a Poisson or Gaussian distribution, wherein the molar ratio of the coordinative chain transfer polymerisation catalyst (CCTP catalyst) to the chain shuttling agent (CSA) is 1 : > 10000, preferably 1 : > 100000.
  • the chain length can be tuned by the amount of olefin oligomerised.
  • the process according to the invention can be carried out in three different modes: a) via a simultaneous process where a CCTP catalyst, a CSA and a CDC (and optionally an activator) are present at the same time, e.g. from the start; or b) via a sequential process where at first a CCTP catalyst, and a CSA (and optionally activator) are present but no CDC and at a later stage the CCTP is deactivated and the CDC is added; or
  • CDC (and optionally activator) are present at the same time, e.g. from the start.
  • CCTP / CSA 1 ⁇ 1000, in particular 1 : 100 to 1 : 500
  • low CDC concentrations CCTP / CDC 1 : 1 to 1 : 2
  • the product distribution can either be tuned by the applied type of CCTP, CSA and CDC and by the ratio of CCTP/CSA CDC or by the applied reaction conditions, mainly pressure and temperature. Increasing ethylene pressure results in higher molecular weight olefins and broader distribution, while increasing temperature yields more short chain olefins with a more narrow distribution.
  • CCTP catalyst coordinative chain transfer polymerisation catalyst
  • CSA chain shuttling agent
  • molar ratio of the coordinative chain transfer polymerisation catalyst (CCTP catalyst) to the chain displacement catalyst (CDC) is 1 : > 2, prefer- ably 1 : 5 to 1 : 10.
  • the oligomerised olefins are being obtained in a mainly Poisson or Gaussian distribution, wherein the molar ratio of the coordinative chain transfer polymerisation catalyst (CCTP catalyst) to the chain shuttling agent (CSA) is 1 : ⁇ 10000, preferably 1 : ⁇ 1000; and the molar ratio of the coordinative chain transfer polymerisation catalyst (CCTP catalyst) to the chain displacement catalyst (CDC) is 1 : ⁇ 10, preferably 1 : ⁇ 4.
  • the olefin is further preferably obtained in a Schulz-Flory distribution, if the molar ratio of the coordinative chain transfer polymerisation catalyst (CCTP catalyst) to the chain shuttling agent (CSA) is 1 : > 1000, preferably 1 : > 10000; and the molar ratio of the coordinative chain transfer polymerisation catalyst (CCTP catalyst) to the chain displacement catalyst (CDC) is 1 : > 10, preferably 1 : 10 to 1 : 20.
  • the process is carried out with a C2 or C3 or C2 and C3 olefin and a pressure of lower than 4 bar, preferably lower than 2 bar, the oligomerised olefin is being obtained predominately in a Schulz-Flory distribution.
  • the Zr/CSA molar ratio preferably is between 1 :300 and 1 :500 and the Zr/CDA molar ratio is between 1 :10 to 1 :20 and the CSA( 1 )/CSA(2) molar ratio is smaller than 4:1.
  • the CDC is subsequently brought in contact with the reaction composition comprising the inactivated CCTP catalyst, the CSA and the oligomerised olefin, the reaction composition not comprising the CDC, wherein the CCTP catalyst is inactivated by heating the reaction composition, most preferably above 120°C or adding catalysts poisons, the catalyst poisons being preferably selected from the group consisting of halogenated metal alkyls alkali and earth alkali salts, the catalysts poisons being selected in a manner that the CCTP catalyst is inactivated but not the CSA and not the CDC to be added.
  • a molar ratio of the coordina- tive chain transfer polymerisation catalyst (CCTP catalyst) to the chain displacement catalyst (CDC) of 1 : 0.05 to 1 : 100, preferably 1 : 1 to 1 : 2.
  • the molar ratio of the coordinative chain transfer polymerisation catalyst (CCTP catalyst) to the chain shuttling agent (CSA) is preferably 1 : > 50000.
  • the CDC catalyst is preferably added at a temperature above 120°C.
  • the sequential reaction mode results in a Schulz-Flory distribution, of the oligomer- ised olefins at low molar ratios of olefin to CSA. Otherwise the sequential reaction mode results in a predominantly Poisson or Gaussian distribution, in particular if the G2 to C3 pressure is greater than 2 bar. In other words in case of sub-sequent addition of CDC and at CSA conversion above 20% increasing amounts of CSA give shorter chain length with a mainly Poisson or Gaussian distribution, below 20% con- version the process will result in a product with a mainly Schulz-Flory distribution. 11.0 Product
  • the oligomerisation is conducted by contacting the monomer(s) and catalyst composition under conditions to produce an oligomer or a polymer having mo- lecular weight (MW [g/mol]) from 56 to 1000000, preferably 56 to 10000, most preferably 84 to 1000.
  • MW [g/mol] mo- lecular weight
  • the distribution of the chain lengths of the olefins obtained can be influenced as follows:
  • the most preferred catalysts according to this invention are complexes IV which are obtained with high selectivity by reacting Zr(NEt2)C (Et20) with Ar-NCN-Ar in a first step to obtain III and reacting III in a second step with 6 moles of methyl magnesium chloride in hexane.
  • the process for the manufacture of a preferred zirconium guanidinato alkyl compound comprises the following steps:
  • Grignard-Reagent preferably used in a 2.8 to 3.2 times molar excess relative to the Zr.
  • the Di- -halogen-bridged bis guanidinato tetrahalogen di zirconium compound is obtainable for example by the following process:
  • Hal is independent from each other Halogen, in particular CI;
  • R 1 ,R 2 being C1 to C40 hydrocarbyl-, optionally comprising one or more het- eroatoms, wherein the heteroatom is not adjacent to the N-Atom;
  • the etherate preferably being a di-(C1- to C6-)hydrocarbylether , in particular a di(C1- to C6-)alkylether, a di-(C2- or C3-)hydrocarbylether, in particular a
  • R 3 ,R 4 independent from each x, y is hydrocarbyl, in particular alkyl, or halogen, wherein R is preferably substituted at the 2 or 6 position of the aryl, and further wherein R is branched at the 2-position;
  • Ar is Aryl, in particular Benzene.
  • a preferred Grignard-Reagent is Alkyl Mg Hal, wherein Hal is independent from each other Halogen, in particular CI, and Alkyl is C1 to C20 alkyl, in particular Methyl or Ethlyl.
  • the Di-p-halogen-bridged bis guanidinato tetrahalogen di zirconium compound preferably is
  • R 1 ,R 2 ,R 3 ,R 4 as defined in claim 18.
  • R 1 ,R 2 being C1 to C40 hydrocarbyl-, optionally comprising one or more het- eroatoms, wherein the heteroatom is not adjacent to the N-Atom;
  • R 3 ,R independent from each x, y is hydrocarbyl, in particular alkyl, or halogen, wherein R is preferably substituted at the 2 or 6 position of the aryl, and further wherein R is branched at the 2-position;
  • the compound obtained according to the above process can be used as a CCTP catalyst.
  • reaction scheme may be outlined as follows:
  • the new well-defined catalyst (structure IV) can therefore improve the earlier described CCTP process by reducing the high molecular weight polymer side products by simultaneously enhancing the catalyst activity.
  • Fig. 1 Reaction scheme illustrating the assumed mechanism of the tandem catalyst oligomerisation process of ethylene via single chain shuttling
  • Fig. 1a Reaction scheme illustrating the assumed mechanism of dual chain shuttling via two CSAs
  • Fig. 2 Molecular structure of III in the formula as displayed above.
  • Fig. 3 Molecular structure of IV as described in the formula as displayed above.
  • Fig. 4 1 H NMR spectrum (C2CI4D2, 120°C) of oligomers obtained with GuaTiMe 3 (I) precatalyst in absence (entry 1 , table 1 , above) and presence of Ni(COD)2 (entry 5, table 2, below). In the absence of a CDC no olefins are observed. With Ni(COD)2 only alpha-olefins were observed.
  • Fig.5 1H NMR spectrum (C2CI4D2, 120°C) of oligomers obtained with GuaZrMe3 (III) precatalyst in absence (entry 2, below, table 1) and presence of Ni(COD)2 (entry 9, above, table 2). In absence of a CDC no olefins are observed.
  • Fig. 12 Influence of DEZn content on the oligomerised olefin obtained with Cp"ApZrMe2 (I) precatalyst in presence of Ni(COD)2 (Table 8, entry 1 , Table 8, entries 3 - 7).
  • Ni(acac)2 - Nickel(ll) acetylacetonate Ni(CsH7O2)2
  • Diethylamido-trichloridozirconium(IV) etherate (0.68 g, 2.0 mmol) and Bis(2,6-diiso- propylphenyl) carbodiimide (0.55 g, 1.5 mmol were dissolved in toluene (100 mL) and stirred overnight at 60°C. After filtration and concentration of the reaction solution, colourless crystals were obtained at -30°C.
  • the catalytic ethylene oligomerisation reactions were performed in a 250 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant).
  • the reactor was ethylene flow controlled and equipped with separated toluene, catalyst and co-catalyst injection systems. During an oligomerisation run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously.
  • the autoclave was evacuated and heated for 1 ⁇ 2 h at 80 °C prior to use. The reactor was then brought to desired temperature, stirred at 500 rpm and charged with 150 mL of toluene.
  • the catalytic ethylene oligomerisation reactions were performed in a 250 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant).
  • the reactor was ethylene flow controlled and equipped with separated toluene, catalyst and co-catalyst injection systems. During a oligomerisation run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously.
  • the autoclave was evacuated and heated for 1 ⁇ 2 h at 80 °C prior to use. The reactor was then brought to desired temperature, stirred at 500 rpm and charged with 150 mL of toluene.
  • the catalytic ethylene oligomerisation reaction was performed in a 1000 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant).
  • the reactor was ethylene flow controlled and equipped with separated toluene, catalyst and co-catalyst injection systems. During the oligo- merisation run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously.
  • the autoclave was evacuated and heated for 1 ⁇ 2 h at 100 °C prior to use. The reactor was then brought to desired temperature, stirred at 500 rpm and charged with 300 mL toluene.
  • Waxy product was collected by filtration (0.2 pm) at 50°C, washed with acidified etha- nol and rinsed with ethanol and acetone on a glass frit. The filtrate was initially dried on air and subsequently in vacuum at 50°C and analyzed via GPC. The permeate was analyzed by GC and /or GC-MS.
  • the catalytic ethylene oligomerisation reaction was performed in a 1000 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant).
  • the reactor was ethylene flow controlled and equipped with separated toluene, catalyst and co-catalyst injection systems. During a oligomerisation run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously.
  • the autoclave was evacuated and heated for 1 ⁇ 2 h at 100 °C prior to use. The reactor was then brought to desired temperature, stirred at 500 rpm and charged with 300 mL toluene.
  • the reactor was depressurized and the reactor flushed with argon. Subsequently the temperature was raised to 00 °C for 1 hour. 8 pmol Bis(cyclooctadienyl)nickel(0), was added to the reactor via a syringe. A temperature of 120 °C was set and maintained via a thermostat. The reactor was pressurized with ethylene again and the reaction monitored until no more ethylene was consumed. The residual TEAL was destroyed by addition of 20 mL of ethanol. A sample was taken from the solution and analyzed via GC with nonane as internal standard.
  • Waxy product was collected by filtration (0.2 pm) at 50°C, washed with acidified ethanol and rinsed with ethanol and acetone on a glass frit. The filtrate was initially dried on air and subsequently in vacuum at 50°C and analyzed via GPC. The permeate was analyzed by GC and /or GC-MS. The distribution of the obtained linear a-olefins are shown in Fig. 9.
  • the catalytic ethylene oligomerization reactions were performed in an 800 ml_ autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant).
  • the reactor was ethylene flow controlled and equipped with separated toluene, catalyst and co-catalyst injection systems. During an oligomerization run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously.
  • the autoclave was evacuated and heated for 1 ⁇ 2 h at 80 °C prior to use. The reactor was then brought to 80 °C, stirred and charged with 250 ml_ of toluene.
  • Waxy product was collected by filtration (0.2 pm) at 50°C, washed with acidified ethanol and rinsed with ethanol and acetone on a glass frit. The permeate was analyzed by GC and /or GC-MS. The distribution of the obtained linear oligomerised alpha olefins are shown in Fig. 9a. Table 7. Ethylene oligomerisation with Y pre-catalysts Ya and Yb, TEAL co-catalyst and methyldialkylammoniumtetrakis(pentafluorophenyl)borate activator. 3
  • ⁇ , ⁇ , ⁇ -trialkylammonium (tetrapentafluorophenyl)borate ([R2NMeH][B(C6F5) ], R C16H33 - C18H37, 6.2 wt-% B(CeF5)4 in Isopar, DOW Chemicals), Bis(1 ,5-cyclooctadi- ene)nickel(O), and Zirconium(IV)chloride are commercially available from abcr GmbH
  • the catalytic ethylene oligomerization reactions were performed in a 300 mL glass autoclave (Buechi) in semi-batch mode (ethylene was added by replenishing flow to keep the pressure constant).
  • the reactor was ethylene flow controlled and equipped with separated toluene, catalyst and co-catalyst injection systems. During an oligomerization run the pressure and the reactor temperature were kept constant while the ethylene flow was monitored continuously.
  • the autoclave was evacuated and heated for 1 ⁇ 2 h at 80 °C prior to use. The reactor was then brought to desired temperature, stirred at 1000 rpm and charged with the desired amount of toluene.

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Abstract

La présente invention concerne un procédé d'oligomérisation d'oléfines, en particulier l'éthylène, par polymérisation par transfert de chaîne et coordination (CCTP) et réaction d'élimination d'alkyle. Un mode de réalisation préféré de la présente invention concerne la CCTP d'oléfines, en particulier l'éthylène, avec l'aide de complexes de guanidinato, amidinato ou hydrocarbyle-2-pyridylamine et de titane, zirconium ou lanthanides, d'un composé du nickel ou de cobalt en tant que catalyseur de déplacement de chaîne (CDC) et d'un ou de plusieurs agents d'échange de chaîne (CSA) tels qu'un métal-alkyle comme groupe principal.
EP16732224.7A 2015-05-13 2016-05-13 Procédé d'oligomérisation d'oléfines par polymérisation par transfert de chaîne et coordination Withdrawn EP3294692A1 (fr)

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EP15167707.7A EP3093280A1 (fr) 2015-05-13 2015-05-13 Procédé d'oligomérisation d'oléfines par polymérisation de coordination de transfert de chaîne et synthèse de catalyseurs
GBGB1512872.1A GB201512872D0 (en) 2015-07-21 2015-07-21 Process for the oligomerisation of olefins by coordinative chain transfer polymerisation and catalyst synthesis
PCT/EP2016/000789 WO2016180538A1 (fr) 2015-05-13 2016-05-13 Procédé d'oligomérisation d'oléfines par polymérisation par transfert de chaîne et coordination

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WO2019205309A1 (fr) * 2018-04-28 2019-10-31 中国科学院青岛生物能源与过程研究所 Complexe métallique catalytique de pyridine-imine de fer ou de cobalt, son procédé de préparation et son application

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US5550303A (en) * 1995-06-02 1996-08-27 Amoco Corporation High efficiency olefin displacement process
ES2177995T3 (es) * 1996-07-23 2002-12-16 Dow Chemical Co Composicion catalitica para la polimerizacion de olefinas que comprende un compuesto del grupo 13.
EP2521613A4 (fr) * 2010-01-04 2014-03-19 Univ Maryland Production évolutive d'hydrocarbures de précision à partir de trialkyaluminium par polymérisation vivante ternaire par transfert de chaîne et coordination
ES2620287T3 (es) * 2012-06-04 2017-06-28 Sasol Olefins & Surfactants Gmbh Complejos de guanidinato y su uso como catalizadores de polimerización de transferencia de cadenas

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